FIELD OF THE INVENTION
[0001] The invention relates to dichlorodiphenyl sulfone pastilles. The invention further
relates to methods of making dichlorodiphenyl sulfone pastilles and methods of poly(aryl
ether sulfone) polymer synthesis incorporating dichlorodiphenyl sulfone pastilles.
BACKGROUND OF THE INVENTION
[0002] Industrial scale polymer synthesis requires high throughput to meet customer demands.
In any such synthesis, the rate at which monomer components are delivered to the polymerization
reactor can place significant limits on the production rate of the polymer. For example,
based upon the monomer composition and morphology used, flow rates of the monomer
to the polymerization reactor may be limited due to partial or total clogging of pipes
conveying the monomer to the polymerization reactor. Poly(aryl ether sulfone) ("PAES")
polymer synthesis involves dichlorodiphenyl sulfone ("DCDPS") as a starting monomer
for the polymerization reaction. Accordingly, improvements in the deliver rate of
the DCDPS monomer to the polymerization reactor can provide significant improvements
in the overall production rate of the PAES polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003]
Fig. 1a is a schematic depiction of a side view of a DCDPS pastille.
Fig. 1b is a schematic depiction of the top view of a DCDPS pastille.
Fig. 2 is a schematic depiction of an apparatus for forming DCDPS pastilles
Fig. 3 is a schematic depiction of a batch polymerization system for the production
of PAES polymers.
Fig. 4 is a schematic depiction of an apparatus for measuring the angle of repose
using the tilting box method.
DETAILED DESCRIPTION OF THE INVENTION
[0004] Described herein are pastilles comprising a dichlorodiphenyl sulfone ("DCDPS"), corresponding
formation methods and methods of synthesizing poly(aryl ether sulfone)s incorporating
the DCDPS pastilles. It was surprisingly discovered that the use of pastilles comprising
DCDPS as monomer source significantly increased the charge rate of the monomer into
polymerization reactors during industrial scale poly(aryl ether sulfone) ("PAES")
synthesis. The DCDPS pastilles can be formed by specifically adapted deposition approaches
to achieve selected pastilles sizes with a narrow size distribution and, furthermore,
can be desirably used in large scale PAES polymer synthesis to significantly improve
polymer throughput.
[0005] Powder formation during DCDPS handling can introduce significant difficulties into
PAES processing and synthesis. DCDPS particles in a powder are generally present as
part of an agglomerated mass, due to short range van der Waals interactions and moisture
uptake form the ambient atmosphere. As used herein, a DCDPS powder refers to a collection
of DCDPS particles having an average primary (un-agglomerated) particle diameter of
from about 5 micrometers ("µm") to 1 mm, preferably to 800 µm, more preferably to
500 µm. Moreover, the extent of agglomeration can increase significantly during relative
short storage times (e.g. three weeks). While PAES synthesis generally involves a
DCDPS monomer source in the form of granules (e.g. generally spherical having a diameter
of from about 2 millimeters ("mm") to about 5 mm), significant quantities of DCDPS
powders are also present, due to attrition (breakage or cracking of the DCDPS granules)
during shipping, storage, and handling. Furthermore, in large scale PAES synthesis,
the DCDPS granules are conveyed from a storage bin to the polymerization reaction
vessel, during which further DCDPS powder generation occurs as described above. The
DCDPS powders (e.g. due to attritioning) tend to agglomerate and reduce the flow of
the DCDPS granules to the polymerization reactor because it promotes clogging of transport
pathways (
e.g. pipes) connecting the DCDPS storage vessel with the polymerization reactor. Correspondingly,
PAES synthesis is generally performed at a relatively reduced rate to accommodate
the reduced DCDPS flow (and to attempt to lessen the amount of clogging). Additionally,
any solid flow blockage can upset the stoichiometric ratio control of the monomer
feeds as well. The reduced production concomitantly increases the storage time of
the DCDPS monomer source, exacerbating the problem of powder agglomeration.
[0006] It was surprisingly found that the use of DCDPS pastilles in the DCDPS processing
allowed for increased DCDPS monomer flow and correspondingly increased production
throughput of PAES polymers during industrial scale synthesis. The DCDPS pastilles
described herein have increased structural integrity relative to DCDPS granules, resulting
in significantly less generation of powders (due to attrition) and a significantly
increased monomer flow rate from the DCDPS storage vessel to the PAES polymerization
reactor. The flowability of the DCDPS pastilles can be measured by measuring the angle
of repose. The DCDPS pastilles described herein have an angle of repose of no more
than 35 degrees or no more than 30 degrees. In additional or alternative embodiments,
the DCDPS pastilles have an angle of repose of at least about 10 degrees, at least
about 15 degrees, or at least about 20 degrees. The angle of repose can be measured
using the tilting box method. Fig. 4 is a schematic depiction of an apparatus for
measuring the angle of repose using the tilting box method. Tilting box apparatus
400 includes level surface 402 and tilt box 404. Tilt box 404 is made of clear acrylic
and has a length of 155 mm a width of 105 mm and a height of 20 mm. The dimensions
of the length and height of tilt box 404 are indicated by double-headed arrows 406
and 408, respectively. The dimension of the width is perpendicular to the dimensions
of the length and the width. When tilt box 404 and level surface 402 are in contact
(parallel to each other, 0°), 25 g of sample 410 is evenly distributed in tilt box
404 to form a substantially flat layer. Tilt box 404 is rotated about axis 412 (perpendicular
to the dimension of length and width) along direction 414 at a rate of 3 °/second.
When sample 410 began to slide by visual detection, the rotation of tilt box 404 was
stopped and the angle between the bottom of tilt box 404 and level surface 402 was
measured using angle measurement device 416. Measuring device 412 can be an inclinometer,
protractor or any other device known in the art as suitable for measuring angles.
The measurement procedure is done 3 times for each sample 410, and the results are
averaged.
[0007] Furthermore, it was discovered that DCDPS pastilles having selected sizes and relatively
narrow size distributions could be formed using specifically adapted processing approaches.
Traditionally, pastille formation involves processing of higher viscosity material,
for which control of pastille size is easily obtainable using a deposition approach
because of the reduced flow rate material. However, low viscosity organic material,
such as DCDPS, presents significant processing challenges during deposition because
of the increased flow of the molten material. The increased flow can translate into
undesirable loss of control on the physical dimensions of the formed pastilles. As
described in detail below, it was found that by implementing a specifically adapted
deposition to control the solidification rate of DCDPS during pastille formation,
tight control of pastille size and size distribution can be achieved.
The Dichlorodiphenyl sulfone Pastilles
[0008] The pastilles of interest herein comprises at least 50 wt% of a DCDPS, relative to
the total weight of the pastille. In some embodiments, the pastilles contain at least
60 wt.%, at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at
least 85 wt.%, at least 90 wt.%, at least 99 wt.%, at least 99.9 wt.% or at least
99.99 wt.% of the DCDPS.
[0009] DCDPS is represented by the following formula:

where R
1 and R
2, at each instance, are independently selected from the group consisting of a halogen,
an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid,
an ester, an amide, an imide, an alkali or an alkaline earth metal sulfonate, an alkyl
sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an
amine and a quaternary ammonium; i and j are independently selected integers from
0 to 4, and X
1 and X
2 are independently selected halogens. As used herein, a halogen refers to any one
of F, Cl, Br, I and At. In some embodiments, the DCDPS is represented by the following
formula:

In some such embodiments, i and j are zero. In additional or alternative embodiments,
X
1 and X
2 are independently selected from Cl and F, preferably X
1 and X
2 and Cl.
[0010] The pastilles have a hemispherical or compressed hemispherical morphology. Referring
to Fig. 1, pastille 100 can be characterized by a height (
e.g. major axis perpendicular to the plane of the base), H, and a width (
e.g. major axis in the plane of the base), W. For hemispherical pastilles, the height
and width can both be defined by the radius of the hemisphere. Compressed hemispheres
have a curvature of surface 102 that is, on average, less than the curvature of a
hemisphere having a radius equal to the height of the compressed hemisphere. A collection
of pastilles can have an average height of at least about 0.1 mm, at least about 0.5
mm, at least about 0.6 mm, at least about 0.7 mm, at least about 0.8 mm, or at least
about 0.9 mm. Additionally or alternatively, the pastilles in the collection of pastilles
have an average height of from about 1 mm to about 4 mm, to about 3 mm or to about
2 mm. Additionally or alternatively, the pastilles can have an average width of from
about 1 mm to about 5 mm or from 2 mm to about 4 mm. In some embodiments, the ratio
of the width to height ("aspect ratio") for a collection of pastilles can be from
about 1.8 to about 2.2.
[0011] A collection of pastilles can have a relative narrow size distribution, in conjunction
with the average sizes (height, width and aspect ratio) described above. In some embodiments,
at least about 90 percent, at least about 95 percent, at least about 97% or at least
about 99% of the individual pastilles in a collection of pastilles have a height greater
than about 80 percent of the average width and less than about 120 percent of the
average width. In some embodiments, at least about 90 percent, at least about 95 percent,
at least about 97% or at least about 99% of the individual pastilles in a collection
of pastilles have a height greater than about 80 percent of the average height and
less than about 120 percent of the average height. In some embodiments, at least about
90 percent, at least about 95 percent, at least about 97% or at least about 99% of
the individual pastilles in a collection of pastilles have an aspect ratio greater
than about 80 percent of the average aspect ratio and less than about 120 percent
of the average aspect ratio.
[0012] In some embodiments, the collection of pastilles can have a weight of at least about
0.5 kg, at least about 1 kg, at least about 5 kg, at least about 10 kg, at least about
20 kg, at least about 40 kg, at least about 100 kg or at least about 200 kg. In some
embodiments, the collection of pastilles can have a weight of from about 0.45 kg to
about 45 kg, from about 4.5 kg to about 45 kg or from about 4.5 kg to about 22.6 kg.
In some embodiments, the collection of pastilles can have a weight of from about 135
kg to about 275 kg.
[0013] As noted above, the DCDPS pastilles have increased structural integrity and, correspondingly,
powder generation from breakage during handling is reduced, relative to DCDPS granules.
In some embodiments, a collection of DCDPS pastilles can have a DCDPS powder content
of no more than about no more than about 5 wt.%, no more than about 4 wt.%, no more
than about 3 wt.%, no more than about 2 wt.% or no more than about 1 wt.%, relative
to the total weight of the DCDPS pastilles and DCDPS powder.
Formation of DCDPS Pastilles
[0014] The pastilles described herein can be formed by a deposition process whereby liquid
(
e.g. molten) DCDPS is discretely deposited onto a surface to form DCDPS pastilles. In
general, the temperature difference between the liquid DCDPS prior to deposition and
the temperature of the deposition surface at least partially determines the rate of
solidification (during cooling) of the pastille after it is deposited on the surface.
If the deposited DCDPS solidifies too quickly, the resulting pastille can have undesirable
amounts of internal stress. Larger internal stress can translate into breakage during
transportation and handling, resulting in powder generation and difficulties during
PAES synthesis, as described in detail above. If the deposited DCDPS solidifies too
slowly, tight control of the pastille dimensions (and corresponding size distribution
in a collection of pastilles) is sacrificed due to the increased spread time of the
DCDPS on the surface after deposition.
[0015] Applicant found that by appropriate selection of the liquid DCDPS temperature and
the deposition surface temperature, DCDPS pastilles having a narrow size distribution
and desirable structural integrity can be formed. For the deposition processes of
interest herein, the temperature of the liquid DCDPS is from about Tm + 5° C to about
Tm + 35° C, where Tm is the melting point of DCDPS. Tm of DCDPS is about 148° C. In
some embodiments, the temperature of the liquid DCDPS is from about 155 ° C to about
180° C. The temperature of the deposition surface can be is from about Tm - 80 ° C
to Tm - 110°C or to Tm - 100 °C.
[0016] Fig. 2 shows an embodiment of DCDPS formation apparatus. Formation apparatus 200
includes monomer reservoir 202 and conveyor belt 204. Monomer reservoir 202 contains
liquid DCDPS 206, held at a selected temperature by heating element 208. A portion
of liquid DCDPS 206 is dispensed from nozzle 210 onto conveyor belt 204. Conveyor
belt is maintained at a selected temperature by cooling element 212. In some embodiments,
cooling element 212 can be a water bath or refrigeration device that blows cold air
onto conveyor belt 204. In other embodiments, a stream of water can be sprayed onto
the belt to maintain the belt at a constant temperature. DCDPS pastilles 214 are formed
by solidification as they travel with conveyor belt 204 in the direction 216 (for
clarity, not all pastilles are labelled), where conveyor belt 204 is propelled by
rollers 218.
PAES Polymer and Synthesis
[0017] The synthesis of PAES polymers involves the condensation reaction of a DCDPS monomer
with a diol. As used herein, a PAES polymer refers to any polymer having at least
50 mole % ("mol%") recurring units (R
PAES) according to the following formula:

where R
3 and R
4, at each instance, are independently selected from a halogen, an alkyl, an alkenyl,
an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide,
an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali
or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary
ammonium; k and l are integers ranging from 0 to 4; and T is selected from the group
consisting of a bond, a sulfone group [S(=O)2], and a group -C(R
5)(R
6)-, where R
5 and R
6 are independently selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl,
an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali
or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth
metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium. Preferably,
R
5 and R
6 are preferably methyl groups. In formula (3), R
1, R
2, i and j are the same as those selected in Formulas (1) and (2). Namely, the Formula
(3) reflects the fact that the PAES polymer is formed from the polycondensation of
the DCDPS monomer and a diol, as explained in detail below. As used herein, the dashed
bonds represent a bond to an adjacent recurring unit. In some embodiments, the PAES
polymer has at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%,
at least 95 mol% or at least 99 mol% recurring units (R
PAES).
[0018] In some embodiments, the PAES polymer is represented by the following formula:

In some embodiments in which recurring unit (R
PAES) is represented by Formula (3) or (4), T is a bond (a polyphenylsulfone), -S(=O)
2- (a polyether sulfone) or - C(CH
3)
2- (a polysulfone). In some such embodiments, or in other embodiments according to
Formula (3) or (4), k and l are zero; i and j are zero; or i, j, k and l are zero.
[0019] The recurring unit (R
PAES) of the PAES polymer are formed by the polycondensation reaction of the DCDPS monomer
and a diol monomer of the following formula:

In some embodiments, the diol can be represented by the following formula:

The person of ordinary skill in the art will immediately recognize that the polycondensation
of a DCDPS monomer according to Formula (1) and a diol monomer according to Formula
(5) results in recurring unit (R
PAES) according to Formula (3). The person of ordinary skill in the art will further immediately
recognize that the polydondensation of a DCDPS monomer according to Formula (2) and
a diol monomer according to Formula (6) result in recurring unit (R
PAES) according to Formula (4).
[0020] Synthesis of PAES polymers on the industrial scale involves batch processing, in
which in which the monomers are stored in storage vessels and transported to a polymerization
reactor for each batch polymerization reaction. Fig. 3 is a schematic diagram of a
batch polymerization system for PAES synthesis. Referring to Fig. 3, the batch polymerization
system 300 includes polymerization reactor 302, DCDPS storage vessel 304, and diol
storage vessel 306. Batch polymerization system 300 also includes solvent storage
vessel 308 and activator vessel 310. In one synthesis approach, DCDPS monomer, diol
monomer, solvent, and activator are delivered from DCDPS storage vessel 304, diol
storage vessel 306, solvent storage vessel 308 and activator vessel 310, respectively,
to polymerization reactor 302. DCDPS monomer is delivered through pipe 312, and the
dial, solvent and activator are delivered through pipes 314, 316 and 318, respectively.
The polycondensation reaction is performed by heating the contents of polymerization
reactor to the reaction temperature (about 180° C to about 240 ° C). With respect
to the form of the DCDPS monomer, clogging (and reduced monomer flow) due to agglomerated
DCDPS powder can occur in pipe 312. As noted above, powder in the DCDPS monomer source
can be significantly reduced (and correspondingly DCDPS flow improved) by conveying
DCDPS pastilles to polymerization reactor 302 through pipe 312.
EXAMPLES
[0021] The following examples demonstrate the flow of DCDPS pastilles.
Example 1: Formation of DCDPS Pastilles
[0022] This example demonstrates the formation of DCDPS pastilles.
[0023] To demonstrate performance, dichlorodiphenyl sulfone ("DCDPS") pastilles were formed
using an apparatus similar to that depicted in Fig. 2. In particular, liquid DCDPS,
stored in a heated reservoir and maintained at a temperature from about 160° C to
about 169° C, was metered through a nozzle and deposited onto a conveyor belt, maintained
at a temperature from about 26° C to about 31° C or to about 45° C to form the pastilles.
The pastilles were collected from the conveyor belt and their dimensions were measured.
For each batch, about 20,000 kg of DCDPS pastilles were formed. The average height
and width of the pastilles was measured using a Vernier caliper, sampling 30 randomly
selected pastilles from the batch.
Table 1
Batch No. |
Minimum Width - Maximum Width (mm) |
Average Width (mm) |
Minimum Height - Maximum Height (mm) |
Average Height (mm) |
1 |
2.6 - 3.0 |
2.8 |
1.1 - 1.6 |
1.35 |
2 |
2.7 - 3.5 |
3.1 |
1.3 - 1.6 |
1.45 |
3 |
2.5 - 3.1 |
2.8 |
1.2 - 1.7 |
1.45 |
4 |
2.5 - 3.0 |
2.75 |
1.3 - 1.6 |
1.45 |
[0024] Referring to Table 1, for the batches processed, excellent control of size (height
and width) was obtained, leading to narrow size distributions of the formed DCDPS
pastilles. For example, the average widths of the collections of pastilles from batches
1 to 4 were 2.8 mm, 3.1 mm, 2.8 mm and 2.75 mm, respectively. In each case, 100% of
the pastilles had a width that was greater than about 80% of the average width and
less than about 120% of the average width. Similar results were observed for the height
measurements.
Example 2: Flow Performance of DCDPS Pastilles
[0025] This example demonstrates the improved flow performance of DCDPS pastilles relative
to DCDPS powders.
[0026] To demonstrate flow several samples were formed. Sample 1 was a DCDPS powder. Sample
2 was a collection of DCDPS pastilles, formed as described in Example 1. Samples 3
to 5 consisted of a mixture of DCDPS granules and attrited sulfone granules. The mixture
was reflective of the amount of attrition in DCDPS granules. Samples 3 to 5 respectively
contained 70 wt.%, 65, wt.% and 55 wt.% DCDPS granules, relative to the total weight
of DCDPS in the sample. The DCDPS granules had an average diameter of more than about
4 mm. The balance of each sample consisted of DCDPS powder consisting of DCDPS particles
having an average diameter of less than about 0.8.
[0027] Flow was determined by measuring the angle of repose of the sample collection of
pastilles. The angle of repose was measured using the tilt-box method, as described
in detail above. The sample parameters and angle of repose measurements are displayed
in Table 2.
Table 2
Sample No. |
Pastille Concentration (wt.%) |
Granule Concentration (wt.%) |
Powder Concentration (wt.%) |
Angle of Repose (degrees) |
1 |
0 |
0 |
100 |
≥ 90 |
2 |
100 |
0 |
0 |
30 |
3 |
0 |
70 |
30 |
45 |
4 |
0 |
65 |
35 |
40 |
5 |
0 |
55 |
45 |
45 |
[0028] Referring to Table 2, the flowability of the pure pastilles (sample 2) was significantly
larger, relative to pure powder (sample 1) and granule/powder mixtures (samples 3
to 5).
Example 3: Flow Performance of DCDPS Pastilles in Industrial Scale Processing
[0029] The example demonstrates the improved flow performance of DCDPS pastilles in an industrial
scale PAES synthesis system.
[0030] To demonstrate flow, DCDPS was loaded into a storage bin a delivered, through a pipe,
to a polymerization reactor. The DCDPS was transported through the pipe using air.
The configuration was similar to the PAES synthesis apparatus schematically depicted
in Fig. 3. Three batches were run. Batch 5 and batch 6 consisted of a 1:1 weight ratio
of DCDPS granules to DCDPS pastilles. Batch 7 consisted of DCDPS pastilles alone.
For each batch, the DCDPS material was loaded into the storage bin. The air pressure
was adjusted to its maximum flow rate. The maximum flow rate was the rate that maximized
DCDPS flow rate into the polymerization reactor, prior to the onset of clogging issues.
After clogging onset, the DCDPS flow rate is decreased (or has a negligible increase)
with an increase in air pressure.
[0031] For the batches tested, the batch consisting of DCDPS pastilles alone had significantly
increased charge rates, relative to the batches consisting of a blend of DCDPS granules
and pastilles. In particular, the charge rate of batches 5 and 6 were measured to
be 3,750 and 3,650 pounds per hour ("lbs/hr"), while batch 7 had a charge rate of
5,800 lbs/hr. In other words, the batch having DCDPS pastilles (batch 7) had an increase
charge rate of about 55% to about 59%, relative to the batches having a 1:1 weight
ratio of DCDPS pastilles to DCDPS granules.
1. A collection of pastilles comprising dichlorodiphenylsulfone ("DCDPS").
2. The collection of pastilles of claim 1 comprising an angle of repose from about 10°
to about 80°, preferable 15° to about 45°.
3. The collection of pastilles of either one of claim 1 and 2, wherein the pastilles
have an average height from about 1 mm to about 4 mm, preferably to about 3 mm , more
preferably to about 2 mm.
4. The collection of pastilles of any one of claims 1 to 3, wherein the pastilles have
an average width from about 1 mm to about 5 mm, preferably form about 2 mm to about
4mm.
5. The collection of pastilles of any one of claims 1 to 4, wherein at least about 90
percent, preferably at least about 95 percent, of the pastilles have a width greater
than about 80 percent of the average width and less than about 120 percent of the
average width.
6. The collection of pastilles according to any one of claims 1 to 5, wherein at least
90 percent, preferably at least about 95 percent, of the pastilles have a height that
is greater than about 80 percent of the average height and less than about 120 percent
of the average height.
7. The collection of pastilles according to any one of claims 1 to 6 having an average
aspect ratio of from about 1.8 mm to about 2.2 mm.
8. The collection of pastilles according to any one of claims 1 to 7, comprising no more
than about 5 wt.%, preferably no more than about 4 wt.%, more preferably no more than
about 3 wt.%, still more preferably no more than about 2 wt.%, most preferably no
more than about 1 wt.% of DCDPS powder, relative to the total weight of the DCDPS
pastilles and DCDPS powder.
9. The collection of pastilles according to any one of claims 1 to 8, wherein the DCDPS
is represented by the following formula:

wherein R
1 and R
2, at each instance, are independently selected from the group consisting of a halogen,
an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid,
an ester, an amide, an imide, an alkali or an alkaline earth metal sulfonate, an alkyl
sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an
amine and a quaternary ammonium; i and j are independently selected integers from
0 to 4, and X
1 and X
2 are independently selected halogens.
10. The collection of pastilles according to claim 9, wherein X1 and X2 are independently selected from Cl and F, preferably X1 and X2 are Cl.
11. The collection of pastilles according to any one of claims 1 to 10, wherein the collection
of pastilles has a weight of at least about 1 kg, preferably at least about 10 kg,
more preferably at least about 20 kg, still more preferably at least about 40 kg,
most preferably at least about 100 kg.
12. A method of making the collection of pastilles of any one of claims 1 to 11, the method
comprising depositing liquid DCDPS onto a surface, wherein the liquid DCDPS is at
a temperature of from about Tm + 5° C to about Tm + 35° C; wherein the surface is
at a temperature from about Tm - 80 ° C to Tm - 110 ° C, preferably to Tm - 100 °
C; and wherein Tm is the melting point of DCDPS.
13. A method of synthesizing a PAES polymer, the method comprising:
forming a reaction mixture comprising:
- the collection of DCDPS pastilles of anyone of claims 1 to 11 and
- a diol monomer represented by the following formula:

wherein R3 and R4, at each instance, are independently selected from a halogen, an alkyl, an alkenyl,
an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide,
an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali
or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary
ammonium; k and l are integers ranging from 0 to 4; and T is selected from the group
consisting of a bond, a sulfone group [S(=O)2], and a group -C(R5)(R6)-, where R5 and R6 are independently selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl,
an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali
or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth
metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium
heating the reaction mixture to a temperature between about 180° C to about 240 °
C.
14. The method of claim 13, wherein the PAES polymer is represented by the following formula,

preferably the following formula